Synthesis, structures, and optical properties of ruthenium(II) complexes of the tris(1-pyrazolyl)methane ligand

Benjamin J. Coe, Madeleine Helliwell, Martyn K. Peers, James Raftery, Daniela Rusanova, Koen Clays, Griet Depotter, Bruce S. Brunschwig

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    Four new complex salts [RuIICl(Tpm)(LA) 2][PF6]n [Tpm = tris(1-pyrazolyl)methane; n = 1, LA = pyridine (py) 1 or ethyl isonicotinate (EIN) 2; n = 3, L A = N-methyl-4,4′-bipyridinium (MeQ+) 3 or N-phenyl-4,4′-bipyridinium (PhQ+) 4] have been prepared and characterized. Electronic absorption spectra show intense d → π* metal-to-ligand charge-transfer (MLCT) absorption bands, while cyclic voltammetry reveals a reversible RuIII/II wave, accompanied by quasireversible or irreversible LA-based reductions for all except 1. Single crystal X-ray structures have been obtained for 1•Me2CO, 2, and 3•Me2CO. For 2-4, molecular first hyperpolarizabilities β have been measured in acetonitrile solutions via the hyper-Rayleigh scattering (HRS) technique at 800 nm. Stark (electroabsorption) spectroscopic studies on the MLCT bands in frozen butyronitrile allow the indirect estimation of static first hyperpolarizabilities β0. The various physical data obtained for 3 and 4 are compared with those reported previously for related cis-{RuII(NH3)4}2+ species [ Coe, B. J. et al. J. Am. Chem. Soc. 2005, 127, 4845 ]. TD-DFT calculations on the complexes in 1-4 confirm that their lowest energy absorption bands are primarily RuII → LA MLCT in character, while Ru II → Tpm MLCT transitions are predicted at higher energies. DFT agrees with the Stark, but not the HRS measurements, in showing that β0 increases with the electron-accepting strength of L A. The 2D nature of the chromophores is evidenced by dominant βxxy tensor components. © 2014 American Chemical Society.
    Original languageEnglish
    Pages (from-to)3798-3811
    Number of pages13
    JournalInorganic Chemistry: including bioinorganic chemistry
    Issue number7
    Publication statusPublished - 7 Apr 2014


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